EP3140350B1 - Article moulé par injection - Google Patents

Article moulé par injection Download PDF

Info

Publication number
EP3140350B1
EP3140350B1 EP15718901.0A EP15718901A EP3140350B1 EP 3140350 B1 EP3140350 B1 EP 3140350B1 EP 15718901 A EP15718901 A EP 15718901A EP 3140350 B1 EP3140350 B1 EP 3140350B1
Authority
EP
European Patent Office
Prior art keywords
components
mol
weight
bis
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP15718901.0A
Other languages
German (de)
English (en)
Other versions
EP3140350A1 (fr
Inventor
Maximilian LEHENMEIER
Gabriel Skupin
Martin Bussmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to PL15718901T priority Critical patent/PL3140350T3/pl
Publication of EP3140350A1 publication Critical patent/EP3140350A1/fr
Application granted granted Critical
Publication of EP3140350B1 publication Critical patent/EP3140350B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D43/00—Lids or covers for rigid or semi-rigid containers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D75/00—Packages comprising articles or materials partially or wholly enclosed in strips, sheets, blanks, tubes or webs of flexible sheet material, e.g. in folded wrappers
    • B65D75/28—Articles or materials wholly enclosed in composite wrappers, i.e. wrappers formed by associating or interconnecting two or more sheets or blanks
    • B65D75/30—Articles or materials enclosed between two opposed sheets or blanks having their margins united, e.g. by pressure-sensitive adhesive, crimping, heat-sealing, or welding
    • B65D75/32—Articles or materials enclosed between two opposed sheets or blanks having their margins united, e.g. by pressure-sensitive adhesive, crimping, heat-sealing, or welding one or both sheets or blanks being recessed to accommodate contents
    • B65D75/36—Articles or materials enclosed between two opposed sheets or blanks having their margins united, e.g. by pressure-sensitive adhesive, crimping, heat-sealing, or welding one or both sheets or blanks being recessed to accommodate contents one sheet or blank being recessed and the other formed of relatively stiff flat sheet material, e.g. blister packages, the recess or recesses being preformed
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

  • Such heat-resistant articles are suitable for the production of coffee capsules, covers for hot drinks, cutlery, containers for hot filling and microwave dishes.
  • Filled biodegradable polymer blends containing a soft polymer such as an aliphatic-aromatic polyester (PBAT) and a rigid polymer such as polylactic acid (PLA) are known in the art US 6,573,340 and the WO 2005/063881 known. Furthermore, filled polymer blends of polybutylene succinate (PBS) and PLA from the WO 2013/000847 and from PBAT, PBS and PLA from the EP 1561785 known. Although the known from the last two writings polymer blends are suitable for injection molding, but are not suitable for applications such as coffee capsules, lids for hot drinks or microwave dishes because of their limited heat resistance and mediocre impact strength.
  • PBS polybutylene succinate
  • PLA polybutylene succinate
  • the aim of the present invention was thus to provide injection-molded articles which do not have the abovementioned disadvantages.
  • the goal has been to provide a plastic with a heat distortion resistance sufficient for hot food applications.
  • the impact strength should be sufficiently high for the articles to meet the mechanical requirements imposed on them.
  • aliphatic polyesters i suitable for the invention are in the WO 2010/034711 described in more detail, which is incorporated herein by reference.
  • the synthesis of the described polyester i is preferably carried out in a direct polycondensation reaction of the individual components.
  • the dicarboxylic acid derivatives are reacted together with the diol in the presence of a transesterification catalyst directly to the high molecular weight polycondensate.
  • the copolyester i can also be obtained by transesterification of polybutylene succinate (PBS) with C 6 -C 20 dicarboxylic acids in the presence of diol.
  • PBS polybutylene succinate
  • the catalysts used are usually zinc, aluminum and in particular titanium catalysts.
  • Titanium catalysts such as tetra (isopropyl) orthotitanate and in particular tetraisobutoxy titanate (TBOT) have the advantage over the tin, antimony, cobalt and lead catalysts, such as tin dioctanoate, which are frequently used in the literature, that the residual amounts of the catalyst or secondary product of the catalyst remaining in the product are less toxic are. This fact is particularly important for the biodegradable polyesters because they are released directly into the environment.
  • TBOT tetraisobutoxy titanate
  • the succinic acid or a mixture of dicarboxylic acids is generally heated in the presence of an excess of diol together with the catalyst usually first for a period of about 60-180 min to an internal temperature of 170 to 230 ° C and distilled off any water formed. Subsequently, the melt of the prepolyester thus obtained is usually at an internal temperature of 200 to 250 ° C within 3 to 6 hours at reduced pressure while distilling off released diol to the desired viscosity with a viscosity number (VZ) of 100 to 450 mL / g, and preferably 120 to 250 mL / g condensed.
  • VZ viscosity number
  • the polyesters according to the invention i can be further classified according to the in JP 2008-45117 and EP-A 488 617 produce described method. It has proven to be advantageous first to react the components a to c to form a prepolyester having a VZ of 50 to 100 ml / g, preferably 60 to 80 ml / g and then this with a chain extender id, for example with diisocyanates or with epoxy-containing polymethacrylates in a chain extension reaction to a polyester i with a VZ of 100 to 450 mL / g, preferably 150 to 300 mL / g implement.
  • the acid component ia used is 90 to 100 mol%, based on the acid components a and b, preferably 91 to 99 mol%, and particularly preferably 92 to 98 mol% succinic acid.
  • Succinic acid is available on a petrochemical route and preferably from renewable raw materials such as described for example in EPA 2185682.
  • EPA 2185682 discloses a biotechnological process for the production of succinic acid and 1,4-butanediol from different carbohydrates with microorganisms from the class of Pasteurellaceae.
  • Acid component i-b is used in 0 to 10 mol%, preferably 1 to 9 mol%, and particularly preferably 2 to 8 mol%, based on the acid components i-a and i-b.
  • C 6 -C 20 -dicarboxylic acids b are in particular to be understood as meaning adipic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid and / or arachidonic acid. Preference is given to suberic acid, azelaic acid, sebacic acid and / or brassylic acid.
  • the abovementioned acids are accessible from renewable raw materials. For example, sebacic acid is available from castor oil.
  • Such polyesters are characterized by an excellent biodegradation behavior [ Literature: Polym. Degr. Rod. 2004, 85, 855-863 ].
  • the dicarboxylic acids ia and ib can be used either as the free acid or in the form of ester-forming derivatives.
  • Particularly suitable ester-forming derivatives are the di-C 1 - to C 6 -alkyl esters, such as dimethyl-, diethyl-, di-n-propyl, di-isopropyl, di-n-butyl, diisobutyl, di-t- butyl, di-n-pentyl, di-iso-pentyl or di-n-hexyl esters.
  • Anhydrides of dicarboxylic acids can also be used.
  • the dicarboxylic acids or their ester-forming derivatives can be used individually or as a mixture.
  • the diols 1,3-propanediol and 1,4-butanediol are also available from renewable raw materials. It is also possible to use mixtures of the two diols. Due to the higher melting temperatures and the better crystallization of the copolymer formed, 1,4-butanediol is preferred as the diol.
  • the diol (component ic) becomes the acids (components ia and ib) in a ratio of diol to diacids of 1.0: 1 to 2.5: 1 and preferably 1.3: 1 to 2.2: 1 set.
  • Excess diol are withdrawn during the polymerization, so that sets an approximately equimolar ratio at the end of the polymerization.
  • approximately equimolar is meant a diacid / diol ratio of 0.98 to 1.00.
  • a branching agent id and / or chain extender id selected from the group consisting of: a polyfunctional isocyanate, isocyanurate, oxazoline, carboxylic anhydride such as maleic anhydride, epoxy (in particular an epoxy-containing poly (meth) acrylate), an at least trifunctional alcohol or an at least trifunctional carboxylic acid.
  • no branching, but only chain extenders are used.
  • Suitable bifunctional chain extenders are, for example, toluylene-2,4-diisocyanate, toluylene-2,6-diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthylene-1,5 diisocyanate or xylylene diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate or methylene bis (4-isocyanatocyclohexane) Understood. Particularly preferred are isophorone diisocyanate and especially 1,6-hexamethylene diisocyanate.
  • Aliphatic polyesters i are understood as meaning, in particular, polyesters such as polybutylene succinate (PBS), polybutylene succinate-co-adipate (PBSA), polybutylene succinate-co-sebacate (PBSSe), polybutylene succinate-co-azelate (PBSAz) or polybutylene succinate-co-brassylate (PBSBr).
  • PBS polybutylene succinate
  • PBSA polybutylene succinate-co-adipate
  • PBSSe polybutylene succinate-co-sebacate
  • PBSAz polybutylene succinate-co-azelate
  • PBSBr polybutylene succinate-co-brassylate
  • the aliphatic polyesters PBS and PBSA are marketed by Showa Highpolymer under the name Bionolle® and by Mitsubishi under the name GSPIa®. Recent developments are in the WO 2010/034711 described.
  • the polyesters i generally have a number average molecular weight (Mn) in the range from 5000 to 100,000, in particular in the range from 10,000 to 75,000 g / mol, preferably in the range from 15,000 to 50,000 g / mol, a weight average molecular weight (Mw) of 30,000 to 300,000, preferably 60000 to 200,000 g / mol and a Mw / Mn ratio of 1 to 6, preferably 2 to 4 on.
  • the viscosity number is between 30 and 450, preferably from 100 to 400 g / ml (measured in o-dichlorobenzene / phenol (weight ratio 50/50)).
  • the melting point is in the range of 85 to 130, preferably in the range of 95 to 120 ° C.
  • the MVR range according to DIN EN 1133-1 is in the range of 8 to 50 and in particular 15 to 40 cm 3/10 min (190 ° C, 2.16 kg).
  • polyesters ii are meant linear, chain-extended and optionally branched and chain-extended polyesters, such as in the WO 96/15173 until 15176 or in the WO 98/12242 to which reference is expressly described. Mixtures of different partially aromatic polyesters are also possible. interesting recent developments are based on renewable raw materials (see WO 2010/034689 ). In particular, polyesters ii are products such as ecoflex® (BASF SE).
  • Suitable aliphatic diacids and the corresponding derivatives ii-a are generally those having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms. They can be both linear and branched. In principle, however, it is also possible to use dicarboxylic acids having a larger number of carbon atoms, for example having up to 30 carbon atoms.
  • 2-methylglutaric acid, 3-methylglutaric acid, ⁇ -ketoglutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, brassylic acid, suberic acid (suberic acid), and itaconic acid may be used singly or as a mixture of two or more thereof.
  • Adipic acid, azelaic acid, sebacic acid, brassylic acid or their respective ester-forming derivatives or mixtures thereof are preferably used. Particular preference is given to using adipic acid or sebacic acid or their respective ester-forming derivatives or mixtures thereof.
  • aliphatic-aromatic polyesters polybutylene adipate terephthalate (PBAT), polybutylene sebacate terephthalate (PBSeT).
  • PBAT polybutylene adipate terephthalate
  • PBSeT polybutylene sebacate terephthalate
  • aromatic dicarboxylic acids or their ester-forming derivatives ii-b may be used singly or as a mixture of two or more thereof. Particularly preferred is terephthalic acid or its ester-forming derivatives such as dimethyl terephthalate used.
  • the diols ii-c - 1,4-butanediol and 1,3-propanediol - are available as a renewable raw material. It is also possible to use mixtures of the diols mentioned.
  • a branching agent and / or 0.05 to 1% by weight preferably 0.1 to 1.0% by weight, based on the total weight of the polyester, of a chain extender (ii-d).
  • the polyesters ii generally have a number average molecular weight (Mn) in the range from 5000 to 100,000, in particular in the range from 10,000 to 75,000 g / mol, preferably in the range from 15,000 to 38,000 g / mol, a weight average molecular weight (Mw) of 30,000 to 300,000, preferably 60000 to 200,000 g / mol and a Mw / Mn ratio of 1 to 6, preferably 2 up to 4.
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • the viscosity number is between 50 and 450, preferably from 80 to 250 g / ml (measured in o-dichlorobenzene / phenol (weight ratio 50/50).)
  • the melting point is in the range of 85 to 150, preferably in the range of 95 to 140 ° C. ,
  • MVR Melt volume rate
  • EN ISO 1133-1 DE 190 ° C, 2.16 kg weight
  • the acid numbers according to DIN EN 12634 are generally from 0.01 to 1.2 mg KOH / g, preferably from 0.01 to 1.0 mg KOH / g and particularly preferably from 0.01 to 0.7 mg KOH / g ,
  • PLA polylactic acid
  • Preferred polylactic acids are, for example, NatureWorks® 6201 D, 6202 D, 6251 D, 3051 D and in particular 3251 D and crystalline polylactic acid types from NatureWorks.
  • the polylactic acid iii is used in a percentage by weight, based on the components i and iv, of 15 to 24%, preferably 15 to 20%.
  • the polylactic acid iii forms the disperse phase and the polyester i is continuous or part of a co-continuous phase.
  • Polymer blends with polyester i in the continuous phase or as part of a co-continuous phase have a higher heat resistance than polymer blends in which polylactic acid iii forms the continuous phase.
  • the ratio of component i to component iii in the compound from which the articles are manufactured should be 2.2 to 3.2 and preferably 2.5 to 3.1.
  • at least one mineral filler iv selected from the group consisting of: chalk, graphite, gypsum, conductive carbon black, iron oxide, calcium chloride, dolomite, kaolin, silica (quartz), sodium carbonate, titanium dioxide, silicate, wollastonite, mica, montmorillonite, talc and mineral fibers.
  • Chalk and talc are particularly preferred as fillers. Interestingly, it has been found that the addition of chalk can further improve the biodegradability of the articles. Talcum in turn can increase the modulus of elasticity more effectively and improve its heat resistance.
  • the compound according to the invention of components i to iv may contain further additives known to the person skilled in the art.
  • plastics technology such as stabilizers; Nucleating agents such as the already mentioned mineral fillers iv or crystalline polylactic acid; Lubricants and release agents such as stearates (especially calcium stearate); Plasticizers such as citric acid esters (especially acetyl tributyl citrate), glyceric acid esters such as triacetylglycerol or ethylene glycol derivatives, surfactants such as polysorbates, palmitates or laurates; Waxes such as erucic acid amide, stearic acid amide or behenamide, beeswax or beeswax esters; Antistatic, UV absorber; UV-stabilizer; Antifog agents or dyes.
  • the additives are used in concentrations of from 0 to 2% by weight, in particular from 0.1 to 2% by weight, based on the compound i to iv according to the invention.
  • Plasticizers may be contained in 0.1 to 10 wt .-% in the inventive compound i to iv.
  • biodegradable for a substance or a substance mixture is fulfilled if this substance or the substance mixture according to DIN EN 13432 has a percentage degree of biodegradation of at least 90% after 180 days.
  • biodegradability causes the polyester (mixtures) to decompose in a reasonable and detectable time.
  • Degradation can be effected enzymatically, hydrolytically, oxidatively and / or by the action of electromagnetic radiation, for example UV radiation, and is usually effected for the most part by the action of microorganisms such as bacteria, yeasts, fungi and algae.
  • the biodegradability can be quantified, for example, by mixing polyesters with compost and storing them for a certain period of time. For example, according to DIN EN 13432 (referring to ISO 14855), CO 2 -free air is allowed to flow through ripened compost during composting and is subjected to a defined temperature program.
  • biodegradability is determined by the ratio of the net CO 2 release of the sample (after subtraction of CO 2 release by the compost without sample) to the maximum CO 2 release of the sample (calculated from the carbon content of the sample) as a percentage defined as biodegradation.
  • Biodegradable polyesters mixtures usually show clear degradation phenomena such as fungal growth, cracking and hole formation after only a few days of composting.
  • Injection molding which is also referred to as injection molding or injection molding is a molding process that is used very often in plastics processing. In injection molding can be produced very economically direct usable moldings in large quantities. The procedure is simplified as follows: In an injection molding machine consisting of a heatable cylinder in which the worm shaft rotates, the respective thermoplastic material ("molding compound”) is melted and injected into a mold made of metal (“tool"). The cavity of the tool determines the shape and surface texture of the finished part. Today, parts of well under one gram can be produced in the double-digit kilogram range.
  • Injection molding can produce commodities with high accuracy economically and in a short time.
  • the nature of the surface of the respective component can be chosen almost freely by the designers. From smooth surfaces for optical applications, to grooving for touch-friendly areas, to patterns or engravings, a variety of surface structures can be visualized.
  • the injection molding process is suitable for economic reasons, especially for the production of larger quantities, such as packaging items.
  • Items such as candy box inserts, game board inserts, folding blisters for all kinds of small items on perforated grid walls in retail, yoghurt or margarine cups are widely used.
  • a preferred item are lids for coffee cups or other cups for hot drinks, as well as containers for filling hot food.
  • a particularly preferred injection molded article is the coffee capsule.
  • This container is filled with a powdered food, in particular coffee powder or a mixture of powdered foods.
  • Under food is understood in addition to coffee, tea, milk, cocoa and soup extracts.
  • the shape of the container can be rotationally symmetrical, conical, spherical, as well as angular, but preferably rotationally symmetric and mainly cylindrical.
  • This container serves for a storage of the / the food and for preparing an aqueous hot beverage which is produced by the passage of hot water (between 60 and 100 ° C) in a subsequent step.
  • the water flowing through dissolves when flowing through the container flavors and bitter substances and thus forms the hot drink.
  • the container is to be manufactured by injection molding.
  • the wall thickness of the flat film used for this purpose, from which the container / s are produced has a thickness of 100 to 1000 .mu.m, preferably 250 to 800 .mu.m, and in particular from 155 to 550 microns.
  • the article may consist of one and preferably of several layers. At least one layer contains the compound of components i) to described above iv). Another layer of the finished shaped container preferably forms a barrier-forming layer.
  • the multilayer structure can be produced by multilayer extrusion in flat film production, as well as applied after the flat film production as a layer: for example by extrusion, printing, spraying or sputtering, in principle with the application of a dispersion, a lacquer or another polymer-based or polymer-containing Systems or the application of a metallic or oxide-containing layer, but preferably by a polymer-based or metallized layer.
  • polyglycolic acid PGA
  • polyhydroxyalkanoates PHA
  • PVB poly-3-hydroxybutyrate
  • PVB poly-3-hydroxybutyrate-co-3-hydroxyvalerate
  • PVB poly-3-hydroxybutyrate-co-3-hydroxyhexanoate
  • EVOH ethylene vinyl alcohol
  • This barrier layer is characterized by an oxygen transmission rate (OTR) measured on the entire film composite after container production according to ASTM D1434 of 0 to 1000 g / m 2 / d, and a water vapor transmission rate according to ASTM F1249 from 0 to 1000 g / m 2 / d, and preferably a simultaneous aroma barrier.
  • OTR oxygen transmission rate
  • the good oxygen barrier or aroma barrier can also be achieved by means of an outer packaging for one or more coffee capsules.
  • Suitable overpacks may be barrier film coated plastic films or paper sheets.
  • compounds of components i particularly preferably 14 to 40 cm are to iv with a MVR (190 ° C, 2.16 kg) according to ISO 1133-1 from 01.03.2012 from 8 to 50 cm 3/10 min, 3/10 min.
  • the molecular weights Mn and Mw of the partly aromatic polyesters were determined by SEC according to DIN 55672-1: eluent hexafluoroisopropanol (HFIP) + 0.05% by weight of trifluoroacetic acid Ka salt; The calibration was done with narrow polymethyl methacrylate standards.
  • the determination of the viscosity numbers was carried out according to DIN 53728 Part 3, January 3, 1985, capillary viscometry.
  • a micro Ubbelohde viscometer, type M-II was used.
  • the solvent used was the mixture: phenol / o-dichlorobenzene in a weight ratio of 50/50.
  • the modulus of elasticity was determined by means of a tensile test on tensile bars with a thickness of about 420 ⁇ m in accordance with ISO 527-3: 2003.
  • the Charpy impact strength was determined according to DIN EN 179-1 / 1 eU: 2000 + Amd.A (measured at 23 ° C., 50% relative humidity).
  • the specimen 80mm x 10mm x4mm
  • the specimen stored close to its Ends as a horizontal bar is stressed by a single stroke of a pendulum, with the impact line in the middle between the two specimen abutments and (the specimen) at a high, nominally constant speed (2.9 or 3.8 m / s ) is bent.
  • the heat resistance HDT-B was determined according to DIN EN ISO 75-2: 2004-9. A standard specimen is subjected to a three-point bend under constant load to produce a bending stress (HDT / B 0.45 MPa), which is specified in the relevant part of this International Standard. The temperature is increased at a uniform speed (120 K / h), and the temperature value at which a predetermined standard deflection corresponding to the fixed bending elongation increase (0.2%) is reached is measured.
  • the compounds listed in Table 1 were produced on a Coperion MC 40 extruder. The temperatures at the outlet were set to 250 ° C. Subsequently, the extrudate was granulated under water. Following granule production, the granules were dried at 60.degree.
  • Examples 2 and 3 show a significantly improved impact strength compared to V1, while the heat distortion resistance (HDT / B) remains at a very high level.
  • Higher amounts of aliphatic-aromatic polyester ii-2 lead to injection moldings with unsatisfactory dimensional stability (HDT / B).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Composite Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (10)

  1. Article moulé par injection ayant une température HDT-B selon DIN EN ISO 75-2:2004-9 de 79 à 105 °C, contenant :
    i) 47 à 59 % en poids, par rapport au poids total des composants i à iv, d'un polyester biodégradable contenant :
    i-a) 90 à 100 % en moles, par rapport aux composants a à b, d'acide succinique ;
    i-b) 0 à 10 % en moles, par rapport aux composants a à b, d'un ou de plusieurs acides dicarboxyliques en C6-C20 ;
    i-c) 98 à 102 % en moles, par rapport aux composants a à b, de 1,3-propanediol ou de 1,4-butanediol ;
    i-d) 0 à 1 % en poids, par rapport aux composants a à c, d'un allongeur de chaîne ou d'un agent de ramification ;
    ii) 3 à 14 % en poids, par rapport au poids total des composants i à iv, d'un polyester aliphatique-aromatique contenant :
    ii-a) 30 à 70 % en moles, par rapport aux composants ii-a à ii-b, d'un acide dicarboxylique en C6-C18 ;
    ii-b) 30 à 70 % en moles, par rapport aux composants ii-a à ii-b, d'acide téréphtalique ;
    ii-c) 98 à 100 % en moles, par rapport aux composants ii-a à ii-b, de 1,3-propanediol ou de 1,4-butanediol ;
    ii-d) 0 à 1 % en poids, par rapport aux composants a à c, d'un allongeur de chaîne ou d'un agent de ramification ;
    iii) 15 à 24 % en poids, par rapport au poids total des composants i à iv, d'acide polylactique ;
    iv) 10 à 35 % en poids, par rapport au poids total des composants i à iv, d'au moins une charge minérale ; pour le mélange des composants i à iv, le rapport entre le composant i et le composant iii dans le mélange étant de 2,2 à 3,2, et le MVR selon DIN EN 1133-1 du 01.03.2012 (190 °C, 2,16 kg) du mélange étant de 8 à 50 cm3/10 minutes.
  2. Article selon la revendication 1, dans lequel le rapport entre le composant i et le composant iii est de 2,5 à 3,1.
  3. Article selon la revendication 1 ou 2, dans lequel le polyester i présente un MVR selon DIN EN 1133-1 du 01.03.2012 (190 °C, 2,16 kg) de 15 à 40 cm3/10 minutes.
  4. Article selon les revendications 1 à 3, dans lequel le polyester ii présente un MVR selon DIN EN 1133-1 du 01.03.2012 (190 °C, 2,16 kg) de 5 à 15 cm3/10 minutes.
  5. Article selon les revendications 1 à 4, dans lequel l'acide polylactique iii présente un MVR selon DIN EN 1133-1 du 01.03.2012 (190 °C, 2,16 kg) de 30 à 40 cm3/10 minutes.
  6. Article selon les revendications 1 à 5, qui comprend au moins 20 % en poids, par rapport au poids total des composants i à iv, d'une charge minérale iv.
  7. Article selon la revendication 5, dans lequel la charge iv est le talc.
  8. Article selon l'une quelconque des revendications 1 à 7, ayant une résistance aux impacts Charpy selon DIN EN 179-1/1eU:2000 de plus de 80 kJ/m2.
  9. Article selon l'une quelconque des revendications 1 à 8, ayant un volume de remplissage de 1 à 80 ml, et un taux de transmission de l'oxygène selon ASTM D1434 de 0 à 1 000 g/m2/j, approprié pour la fabrication de capsules de café.
  10. Utilisation d'un article selon l'une quelconque des revendications 1 à 8 en tant que vaisselle pour le micro-onde ou couvercle de gobelets pour boissons chaudes.
EP15718901.0A 2014-05-09 2015-04-29 Article moulé par injection Active EP3140350B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL15718901T PL3140350T3 (pl) 2014-05-09 2015-04-29 Wyrób formowany wtryskowo

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP14167691 2014-05-09
EP14191986 2014-11-06
PCT/EP2015/059303 WO2015169660A1 (fr) 2014-05-09 2015-04-29 Article moulé par injection

Publications (2)

Publication Number Publication Date
EP3140350A1 EP3140350A1 (fr) 2017-03-15
EP3140350B1 true EP3140350B1 (fr) 2018-06-27

Family

ID=53008517

Family Applications (1)

Application Number Title Priority Date Filing Date
EP15718901.0A Active EP3140350B1 (fr) 2014-05-09 2015-04-29 Article moulé par injection

Country Status (10)

Country Link
US (1) US9914831B2 (fr)
EP (1) EP3140350B1 (fr)
CN (1) CN106661313B (fr)
AU (1) AU2015257900B2 (fr)
CA (1) CA2948422C (fr)
ES (1) ES2688824T3 (fr)
MX (1) MX376192B (fr)
PL (1) PL3140350T3 (fr)
PT (1) PT3140350T (fr)
WO (1) WO2015169660A1 (fr)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2688824T3 (es) * 2014-05-09 2018-11-07 Basf Se Artículos moldeados por inyección
CN107974050A (zh) * 2016-10-21 2018-05-01 中国石油化工股份有限公司 一种聚酯组合物及其制备方法
IT201700022439A1 (it) * 2017-02-28 2018-08-28 Novamont Spa Composizione polimerica per film ad elevata disintegrabilita’
WO2018210609A1 (fr) * 2017-05-17 2018-11-22 Basf Se Mélange de polyester résistant aux chocs
EP3668926B8 (fr) * 2017-08-15 2022-03-30 Basf Se Article moulé par injection comprenant des silicates à surface modifiée
WO2019034517A1 (fr) 2017-08-15 2019-02-21 Basf Se Article moulé par injection contenant des silicates modifié par un silane
US12398265B2 (en) 2018-12-06 2025-08-26 Basf Se Method for preparing a (co)polyester
EP3696232B1 (fr) * 2019-02-15 2021-08-25 Basf Se Article moulé par injection
IT202000007963A1 (it) * 2020-04-15 2021-10-15 Novamont Spa Composizione polimerica biodegradabile per la realizzazione di articoli stampati.
FR3110900B1 (fr) * 2020-05-29 2022-07-22 My Tea Cup Ag Capsules biodegradables
TW202323607A (zh) 2021-09-10 2023-06-16 瑞士商海洋安全公司 纖維
TW202502959A (zh) 2023-03-15 2025-01-16 瑞士商海洋安全公司 用於三維印刷之纖維及長絲
TW202442413A (zh) 2023-03-15 2024-11-01 瑞士商海洋安全公司 注射模製物件
EP4624529A1 (fr) * 2024-03-28 2025-10-01 Basf Se Composition de polymère biodégradable pour moulage par injection et thermoformage

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0488617B1 (fr) 1990-11-26 1997-09-17 Showa Highpolymer Co., Ltd. Une méthode pour la préparation de polyester saturé
DE4440858A1 (de) 1994-11-15 1996-05-23 Basf Ag Biologisch abbaubare Polymere, Verfahren zu deren Herstellung sowie deren Verwendung zur Herstellung bioabbaubarer Formkörper
DE4440837A1 (de) 1994-11-15 1996-05-23 Basf Ag Biologisch abbaubare Polymere, Verfahren zu deren Herstellung sowie deren Verwendung zur Herstellung bioabbaubarer Formkörper
DE4440850A1 (de) 1994-11-15 1996-05-23 Basf Ag Biologisch abbaubare Polymere, Verfahren zu deren Herstellung sowie deren Verwendung zur Herstellung bioabbaubarer Formkörper
DE4440836A1 (de) 1994-11-15 1996-05-23 Basf Ag Biologisch abbaubare Polymere, Verfahren zu deren Herstellung sowie deren Verwendung zur Herstellung bioabbaubarer Formkörper
US6046248A (en) 1994-11-15 2000-04-04 Basf Aktiengesellschaft Biodegradable polymers, the preparation thereof and the use thereof for producing biodegradable moldings
DE19638488A1 (de) 1996-09-20 1998-03-26 Basf Ag Biologisch abbaubare Polyester
US6573340B1 (en) 2000-08-23 2003-06-03 Biotec Biologische Naturverpackungen Gmbh & Co. Kg Biodegradable polymer films and sheets suitable for use as laminate coatings as well as wraps and other packaging materials
US20060148969A1 (en) * 2002-10-22 2006-07-06 Kazuya Tanaka Resin composition and molded object formed from the resin composition
ES2718635T3 (es) 2003-12-22 2019-07-03 Novamont Spa Combinaciones de polímeros con reología mejorada y resistencia al impacto sin entalla mejorada
US7927532B2 (en) * 2006-02-28 2011-04-19 Cereplast, Inc. Biodegradable nano-polymer compositions and biodegradable articles made thereof
JP5176415B2 (ja) 2006-07-18 2013-04-03 三菱化学株式会社 脂肪族ポリエステルの製造方法
WO2009024294A1 (fr) 2007-08-17 2009-02-26 Basf Se Mannheimia succini producens ddl producteur d'acide succinique microbien
KR101731123B1 (ko) 2008-09-29 2017-04-27 바스프 에스이 지방족 폴리에스테르
CN102165013B (zh) 2008-09-29 2013-04-24 巴斯夫欧洲公司 可生物降解的聚合物混合物
WO2010034710A1 (fr) * 2008-09-29 2010-04-01 Basf Se Polyester aliphatique-aromatique
US20120135169A1 (en) * 2009-05-19 2012-05-31 Robert Tangelder Bioplastics
EP2540779A1 (fr) * 2011-06-30 2013-01-02 Basf Se Article fabriqué par thermoformage ou moulage par injection
US9034945B2 (en) * 2011-06-30 2015-05-19 Basf Se Item produced via thermoforming
EP2551301A1 (fr) * 2011-07-29 2013-01-30 Basf Se Feuille en polyester biodégradable
PT3140349T (pt) * 2014-05-09 2018-10-31 Basf Se Artigos produzidos por termoformação
ES2688824T3 (es) * 2014-05-09 2018-11-07 Basf Se Artículos moldeados por inyección

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
PT3140350T (pt) 2018-10-10
CA2948422C (fr) 2022-05-03
CA2948422A1 (fr) 2015-11-12
WO2015169660A1 (fr) 2015-11-12
US9914831B2 (en) 2018-03-13
MX376192B (es) 2025-03-07
MX2016014712A (es) 2017-02-23
AU2015257900B2 (en) 2018-07-26
PL3140350T3 (pl) 2019-01-31
CN106661313A (zh) 2017-05-10
US20170260387A1 (en) 2017-09-14
ES2688824T3 (es) 2018-11-07
CN106661313B (zh) 2018-10-12
AU2015257900A1 (en) 2016-12-08
EP3140350A1 (fr) 2017-03-15

Similar Documents

Publication Publication Date Title
EP3140350B1 (fr) Article moulé par injection
EP3140349B1 (fr) Article fabriqué par thermoformage
EP2350162B1 (fr) Polyesters aliphatiques
EP2331634B1 (fr) Melanges de polymeres biodegradables
EP2331603B1 (fr) Polyesters aliphatiques-aromatiques
EP2499189B1 (fr) Procédé de fabrication de films rétractables
EP2888323B1 (fr) Mélanges polymères pour la fabrication de pièces moulées par injection à parois minces
DE69908209T2 (de) Polyestergranulate und Verfahren zu ihrer Herstellung
EP3668926B1 (fr) Article moulé par injection comprenant des silicates à surface modifiée
EP2550329B1 (fr) Procédé pour la préparation des films
EP2726549B1 (fr) Article fabriqué par moulage par injection
EP3668921B1 (fr) Article moulé par injection contenant du silicate, modifié par silane
EP3696232B1 (fr) Article moulé par injection
EP2688956A1 (fr) Polyester à base d'acide 2-méthylsuccinique
EP2826817A1 (fr) Mélange de polyester biodégradable
EP2888322B1 (fr) Utilisation de mélanges polymères pour la fabrication de cartouches, de pipettes, de cuvettes ou de porte-pipettes

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20161209

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20180213

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1012296

Country of ref document: AT

Kind code of ref document: T

Effective date: 20180715

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502015004841

Country of ref document: DE

REG Reference to a national code

Ref country code: PT

Ref legal event code: SC4A

Ref document number: 3140350

Country of ref document: PT

Date of ref document: 20181010

Kind code of ref document: T

Free format text: AVAILABILITY OF NATIONAL TRANSLATION

Effective date: 20180824

Ref country code: NL

Ref legal event code: FP

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180927

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180627

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180627

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180627

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180927

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2688824

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20181107

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180627

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180627

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180928

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180627

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180627

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180627

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180627

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180627

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181027

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180627

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502015004841

Country of ref document: DE

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180627

26N No opposition filed

Effective date: 20190328

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180627

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180627

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180627

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190429

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180627

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190429

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180627

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20150429

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180627

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180627

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20250424

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PL

Payment date: 20250415

Year of fee payment: 11

Ref country code: DE

Payment date: 20250428

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20250513

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20250422

Year of fee payment: 11

Ref country code: BE

Payment date: 20250424

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PT

Payment date: 20250409

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20250424

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20250501

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20250417

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20260225

Year of fee payment: 12